WO2004081284A1 - Process for producing paper - Google Patents

Process for producing paper Download PDF

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Publication number
WO2004081284A1
WO2004081284A1 PCT/JP2003/003014 JP0303014W WO2004081284A1 WO 2004081284 A1 WO2004081284 A1 WO 2004081284A1 JP 0303014 W JP0303014 W JP 0303014W WO 2004081284 A1 WO2004081284 A1 WO 2004081284A1
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WO
WIPO (PCT)
Prior art keywords
paper
mass
titanium dioxide
cmc
stock
Prior art date
Application number
PCT/JP2003/003014
Other languages
French (fr)
Japanese (ja)
Inventor
Tomohisa Gondo
Masasuke Watanabe
Kenji Hakuto
Osamu Kitao
Original Assignee
Oji Paper Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oji Paper Co., Ltd. filed Critical Oji Paper Co., Ltd.
Priority to PCT/JP2003/003014 priority Critical patent/WO2004081284A1/en
Priority to AU2003221374A priority patent/AU2003221374A1/en
Priority to CNB038260735A priority patent/CN100373003C/en
Publication of WO2004081284A1 publication Critical patent/WO2004081284A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D21H17/26—Ethers thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/675—Oxides, hydroxides or carbonates

Definitions

  • the present invention relates to a method for producing paper. More specifically, the present invention relates to a method for producing paper containing cellulose fiber, aluminum sulfate, and titanium dioxide, wherein titanium dioxide particles can be contained in paper at a high yield during papermaking. is there. Background art
  • JP-A-5-78997 a method using an amphoteric water-soluble polymer and anionic colloidal silica and / or bentonite (JP-A-9-195197)
  • JP-A-9-195197 a method using an amphoteric water-soluble polymer and anionic colloidal silica and / or bentonite
  • An object of the present invention is to provide a method for producing paper containing cellulose fibers, aluminum sulfate and titanium dioxide, which improves the yield of containing titanium dioxide with respect to the paper and has excellent optical properties and strength properties. It is in.
  • the stock when a paper stock containing cellulose fibers, aluminum sulfate and titanium dioxide is subjected to a papermaking process to make paper, the stock is converted into an aqueous slurry containing the cellulose fibers by carbohydrate.
  • the degree of substitution with the xymethyl group is adjusted to 0.3 to 0.6. It is characterized by being prepared by adding and mixing oxymethylcellulose, and then further adding and mixing aluminum sulfate and titanium dioxide.
  • the amount of said force Rubo Kishimechiruseru port over scan contained in the paper stock in the papermaking process of the present invention 0 the absolute dry weight of the cell opening over cellulose fiber. 0. 5 to 3.0 mass 0/0 It is preferable to control.
  • the amount of the aluminum sulfate contained in the stock is 0.1 to 100% of the absolute dry mass of the cellulose fibers.
  • the amount of the titanium dioxide contained in the stock is 1 to 25 mass of the absolute dry weight of the cellulose fiber.
  • the inventors of the present invention can remarkably improve the yield of titanium dioxide content at the time of papermaking inexpensively, easily, and significantly improve the quality of the obtained paper (such as optical properties and mechanical strength properties). We have been conducting intensive research on ways to improve).
  • the fine particles of titanium dioxide generally have a negative charge, and therefore are considered to be adsorbed on the cellulose fiber sheet (paper) by a static action via a cationic agent.
  • the present inventors have preliminarily added and mixed carboxymethylcellulose whose degree of substitution with carboxymethyl groups has been adjusted to 0.3 to 0.6 in a cellulose fiber-containing aqueous slurry before papermaking.
  • the raw material cellulose fiber used in the method of the present invention is not particularly limited, and generally used known papermaking pulp can be used.
  • chemical pulp such as sulfite pulp, craft pulp, and soda pulp, and semi-chemical pulp Pulp
  • wood pulp such as pulp, pulp, non-wood pulp such as kozo, honey, hemp, etc .
  • deinked pulp manufactured by processing waste paper and unbleached pulp and bleached pulp. Pulp.
  • the titanium dioxide used in the method of the present invention has an average primary particle diameter in the range of 0.1;! To 0.4 ⁇ , and the crystal form is selected from rutile type and anatase type, and these are used alone. Or may be used in combination.
  • Titanium dioxide is preliminarily dispersed in water and then provided for preparation of a stock.
  • a dispersant may be added to prevent reaggregation of particles.
  • the dispersant one or more of sodium hexamethacrylate, sodium pyrophosphate, sodium polyarylate and the like can be used.
  • the amount of titanium dioxide added to the paper stock can be appropriately set according to the quality of the target paper, the intended use, and the like. Generally, it is preferably from 1 to 25% by mass, more preferably from 3 to 20% by mass, based on the absolute dry mass of the cellulose fiber in the stock.
  • the carboxymethylcellulose (hereinafter referred to as CMC) used in the method of the present invention is a cellulose derivative derived from wood pulp or linter pulp as a raw material and reacted with monochloroacetic acid or the like.
  • CMC carboxymethylcellulose
  • carboxyethylcellulose which is a cellulose derivative similar to CMC, the effect is lower than that of CMC and the cost is high. Need not be used as an essential ingredient.
  • the degree of carboxymethyl group substitution (degree of etherification) of the CMC used in the method of the present invention is adjusted to the range of 0.3 to 0.6. Those having a degree of substitution of less than 0.3 are insoluble in water, are not adsorbed on the surface of cellulose fibers, are simply mixed with cellulose fibers, and have a high yield of titanium dioxide on paper. Can't improve. On the other hand, those with a degree of substitution exceeding 0.6 have an excessive number of ionic groups (one CH 2 COO— group) in the molecule, and therefore have a negative charge on the cellulose fiber with a negative charge.
  • CCM adsorbs on the surface of the cell mouth fiber even if the electrolyte is co-existed and the electrostatic repulsion is shielded to some extent due to the strong repulsion and poor affinity with the cellulose fiber. And the yield of titanium dioxide on paper cannot be improved.
  • the degree of carboxymethyl group substitution of CMC can be measured by the method described below.
  • the CMC used in the method of the present invention depends on the properties of the cellulose fibers used. As described above, various polymerization degrees can be produced by the CMC production method, but the viscosity of a 1% aqueous solution is 5 to 16,000 mPa-s (0.1 l). N-NaCl solvent, 25 ° C, B-type viscometer), average polymerization degree of 100 to 4,500, average molecular weight of 20,000 to 100,000 Is preferred.
  • the CMC used in the method of the present invention generally has a carboxylic acid group formed into a sodium salt or a sodium salt of a carboxylic acid.
  • the bean or ray should be a canoleboxymethinoresenorelose-powered bead, but for simplicity, the description of sodium or calcium is omitted, and this is simply referred to as carboxymethylcellulose (CMC).
  • CMC carboxymethylcellulose
  • the CMC used in the method of the present invention includes its sodium salt, potassium salt or ammonium salt, but it is inexpensive, easily available, and highly effective. It is preferable to use a sodium salt.
  • an aqueous solution of CMC is used. If the CMC concentration of this aqueous solution is too high, the viscosity of the CMC aqueous solution is high, and diffusion into the cellulose fiber slurry becomes poor. becomes therefore, it is preferable that CMC concentration is 0.0 1 to 5.0 wt%, more preferably in the range of 0.1 to 3.0 mass 0/0.
  • the solvent for dissolving CMC is generally water, and in the method of the present invention, an aqueous solution of CMC is usually used. However, as long as the CMC is stably dissolved, the solvent may be compatible with water if necessary. Certain solvents such as methanol and ethanol may be mixed with water at a ratio of 10.0 to 30.0%, and if necessary, as long as CMC is stably dissolved. First, an additive such as an electrolyte such as sodium sulfate may be mixed.
  • the amount of CMC added in the method of the present invention should be appropriately set according to the degree of substitution of CMC, the type and use of the paper to be produced, the required performance, etc. However, it is preferably used in an amount of 0.05 to 3.0% by mass, more preferably 0.1 to 1.0% by mass, based on the dry mass of the cellulose fiber. The effect becomes more remarkable as the amount of CMC used increases, but it is 0.05 to 3.0 mass. A sufficient effect can be obtained with the addition amount of / 0 , and if it exceeds 3.0% by mass, the formation of the obtained paper may be poor or the drainage may be insufficient. In addition, the cost of CMC limits its use due to paper applications and economics. If the amount of CMC is less than 0.05% by mass, the effect of improving the yield containing titanium dioxide may be insufficient.
  • the cellulose fiber concentration of the cell mouth fiber slurry is preferably 1.0 to 5.0% by mass in terms of solid content. More preferably, it is 2.0 to 4.0 mass%. If the concentration is too high, stirring may be difficult and mixing may be insufficient.On the other hand, if the concentration is too low, the interaction between cellulose fibers and CMC will be insufficient, and the adsorption of CMC to the surface of cellulose fibers will be insufficient. May be uneven.
  • CMC in preparing the stock, first, CMC is added to an aqueous slurry of cellulose fibers, and then aluminum sulfate and titanium dioxide are added.
  • the order of addition of aluminum sulfate and titanium dioxide may be appropriately determined according to the state of addition during papermaking. After the addition of aluminum sulfate and titanium dioxide, the amount of negative charge on the pulp fiber surface does not increase, and the effect of improving the yield of titanium dioxide cannot be obtained.
  • the amount of titanium dioxide and the amount of aluminum sulfate used as a fixing agent for various papermaking chemicals can be appropriately set according to the type, use, and required quality of the paper. 0.1 to 3.0% by mass based on the dry mass of the fiber , Yo Ri preferably 1.0 to 2.0 mass 0/0. If it is less than 0.1% by mass, the fixing ability of titanium dioxide may be insufficient, and if it exceeds 3.0% by mass, not only is it economically disadvantageous but also
  • the formation of the paper may be poor and the storage stability may be deteriorated.
  • known papermaking agents such as a papermaking paper strength enhancer and a wet paper strength enhancer, a sizing agent, a filler, a retention aid, a dye, an antifoaming agent, a preservative, and a viscosity reducing agent are used. They can be added to the stock as needed, and their type and amount are not particularly limited as long as the quality required for the obtained paper can be satisfied. In order to exert the respective effects of the above papermaking chemicals, it is preferable to add them after the addition of CMC.
  • Papermaking by the method of the present invention can be carried out by using a known wet paper machine, for example, a commercial-scale paper machine such as a fourdrinier-type paper machine, a gap former-type paper machine, a circular net-type paper machine, or a short-mesh type paper machine. And the above-mentioned stock is supplied to this.
  • a commercial-scale paper machine such as a fourdrinier-type paper machine, a gap former-type paper machine, a circular net-type paper machine, or a short-mesh type paper machine.
  • the yield of titanium dioxide on paper obtained by the conventional method can be improved by about 10 points by the method of the present invention.
  • the base paper obtained in this way can be sized using starch, PVA, PAM, etc. with various size presses, roll coaters, etc., of course.
  • a method of performing a size press treatment by increasing the solid concentration of the paste by using a film-metering type size press device is preferably used.
  • various electrolytes as a conductive agent to the surface treatment agent starch, ⁇ ⁇ , PAM, and the like.
  • the electrolyte include sodium sulfate, sodium chloride, and the like.
  • Paper produced by the method of the present invention is used as it is as a product It can also be used as a base paper for paper having a coating composition layer, such as printing paper and information recording paper.
  • a coating composition layer such as printing paper and information recording paper.
  • % means “% by mass” in all cases, and the amount of the additive added to the cellulose fiber slurry is based on the mass of the absolutely dry paper stock. "% By mass”.
  • the measurement was carried out in accordance with JIS SP 8113 and indicated by the breaking length (km).
  • the measurement was performed in accordance with JIS P8138.
  • the stock density and ash content were measured according to TAPPIT 26 9-cm 92.
  • the total stock density in the headbox is HT
  • the total stock density in the tray is WT
  • the 100% fraction of ash in the headbox is F1
  • the percentage of ash in white water is F2.
  • Fiber, fine fiber, filler was calculated according to the following equations.
  • Total stock OPR (%) ⁇ (HT-WT) / HT ⁇ x 1 0 0
  • a 1% solution was prepared using 0.1 N—NaCl as a solvent, and measured at 25 ° C with a B-type viscometer.
  • the degree of substitution of the test carboxymethylcellulose (CMC) was calculated according to the following equation.
  • A represents the amount of 1/10 normal sulfuric acid (ml) consumed by the alcohol in 1 g of the sample
  • a represents the amount of 1/10 normal sulfuric acid added
  • f 1 represents the factor of 1/10 normal sulfuric acid
  • b represents the titer (ml) of 1Z10 normal hydroxide power
  • f2 represents the factor of 1/10 normal potassium hydroxide.
  • M represents the mass (g) of bone dry CMC.
  • Example 1 Softwood bleached pulp and hardwood bleached pulp were mixed in a ratio of 3: 7 using an experimental Niagara Vita and beaten to 400 mL of Canadian Standard Freeness (CSF).
  • Aqueous scan la rie of the pulp fibers (pulp concentration 2.0 mass 0/0)., Degree of substitution 0.4 6 CMC (solids concentration 1. Solution viscosity 2 0 0 TadashiTadashi% m P a ⁇
  • a paper strength agent containing anionic polyacrylamide as a main component (trade name: Polyaclon ST13, manufactured by Misa Ceramics) 0.5% by mass, papermaking Rosin sizing agent for use (trade name: SPE, Arakawa Chemical Industries, Ltd.) 0.3% by mass, cation-modified starch (trade name: Kate 15, National Starch Co., Ltd.) 1.0% by mass, aluminum sulfate Niumu 1.5 mass 0/0, titanium dioxide (particle diameter 0. 2 / m, anatase, trade name: B 1 0 1, Nippon talc Co., Ltd.) 1 7 wt%, was added in the order of the paper A preparation was prepared.
  • paper having a basis weight of 90 g / m 2 was prepared using a square sheet machine for laboratory use, and air-dried indoors.
  • the hand-made sheet was conditioned for 24 hours at 23 ° C. and 50% RH, and then subjected to a quality evaluation test. Table 1 shows the results.
  • Table 1 shows the test results.
  • Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, the amount of CMC added was set to 0.05% by mass based on the absolute pulp mass. Table 1 shows the test results.
  • Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality.
  • the CMC is a CMC with a solution viscosity of 900 mPa * s at a solid concentration of 1% and a degree of substitution of 0.4 (trade name: Cellogen # 412C, manufactured by Daiichi Kogyo Seiyaku ) Was used. Table 1 shows the test results.
  • a handsheet was prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality.
  • the CMC a CMC with a solution viscosity of lOOmPas with a solid content of 1% and a substitution degree of 0.35 was used, and the amount of CMC added to the absolute dry mass of the pulp fiber was 3. 0 mass. /.
  • the amount of aluminum sulfate added was 1.0% by mass. Table 1 shows the test results.
  • Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, the amount of aluminum sulfate added to the absolutely dry mass of pulp fiber was 0.1% by mass.
  • the test results are shown in Table 1 Comparative Example 1 Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, no CMC was added to the stock. Table 1 shows the test results.
  • Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality.
  • the addition of CMC was made after the addition of titanium dioxide. Table 1 shows the test results.
  • Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality.
  • the CMC used was CMC with a degree of substitution of 0.6 (solution viscosity of 500 mPa ⁇ s with a solid concentration of 1%, trade name Serogen HH, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). The addition rate was 3.3%. Table 1 shows the test results.
  • Hand-made sheets were prepared in the same manner as in Example 9, and the obtained paper was tested to evaluate the quality. However, the amount of CMC added was 0.02%. Table 1 shows the test results.
  • a handsheet was prepared in the same manner as in Comparative Example 1, and the obtained paper was tested to evaluate the quality.
  • a retention improver containing a cationic polyacrylamide as a component (trade name: Himolock DR1200H, manufactured by Himo) is based on the absolutely dry pulp fiber content. . 0 4 quality % was added after the addition of titanium dioxide.
  • the test results are shown in Table 1 Comparative Example 5
  • Hand-made sheets were prepared in the same manner as in Comparative Example 1, and the obtained paper was tested to evaluate the quality.
  • the yield improver containing a cationic polyacrylamide as a component (trade name: Percoll 57, manufactured by Kyowa Sangyo Co., Ltd.) is 0.04% by mass based on the absolute dry mass of the pulp fiber.
  • 0.1% by mass of modified bentonite (trade name: Hydrocol 0, manufactured by Kyowa Sangyo Co., Ltd.) were added after addition of titanium dioxide. Table 1 shows the test results.
  • Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, the amount of aluminum sulfate added was 3.5% by mass with respect to the dry mass of the pulp fibers. Table 1 shows the test results.
  • the use of the method of the present invention makes it possible to easily produce titanium dioxide with high yield and excellent paper quality.
  • the yield of titanium dioxide was improved (Example 1 Comparative Example 1).
  • the effect is high compared to the case where the retention improvement system is used (Example 1, Comparative Examples 4 and 5).
  • the lower the degree of substitution of CMC the higher the effect, and when CMC with a degree of substitution of more than 0.6 is used, the effect is remarkably reduced (Examples 1, 5 and Comparative Example 3).
  • the method of the present invention is a method for producing paper that improves the yield of titanium dioxide, provides paper of excellent paper quality, and cleans the papermaking system to improve operability. It has.

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  • Inorganic Chemistry (AREA)
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Abstract

A process for producing paper comprising cellulosic fibers, aluminum sulfate, and titanium dioxide, which includes adding carboxymethyl cellulose having a degree of substitution with carboxymethyl of 0.3 to 0.6 to an aqueous slurry of cellulosic fibers and then adding thereto aluminum sulfate and titanium dioxide to prepare a papermaking stock. Thus, the content of titanium dioxide in the paper produced through a papermaking step can be improved.

Description

明 細 書 紙の製造方法 技術分野  Description Paper manufacturing method Technical field
本発明は、 紙の製造方法に関するものである。 更に詳しく述べる ならば、 本発明は、 セルロース繊維、 硫酸アルミニウム及び二酸化 チタンを含み、 抄紙の際に二酸化チタン粒子を紙に高い歩留ま りで 含有させるこ とのできる紙の製造方法に関するものである。 背景技術  The present invention relates to a method for producing paper. More specifically, the present invention relates to a method for producing paper containing cellulose fiber, aluminum sulfate, and titanium dioxide, wherein titanium dioxide particles can be contained in paper at a high yield during papermaking. is there. Background art
紙の白色度及び不透明度などの光学特性、 或いは紙の印刷適性を 向上させるために、 従来、 炭酸カルシウム、 二酸化チタン、 水和ケ ィ酸 (ホワイ トカーボン） 、 タルク、 ク レー、 カオリ ン、 尿素一ホ ルマリ ンポリマーなどの微粒子等の製紙用填料が使用されている。 これらの填料のなかでも二酸化チタンは光散乱能が高いという性能 を有するため、 高不透明度を紙に付与する 目的で広く用いられてい る。 しかし、 二酸化チタンは、 他の製紙用填料と比較しても、 その 粒子径が小さいために、 抄紙機で抄紙する際の歩留ま りが極めて低 いことが大きな問題となっている。 填料の歩留まりが低いと、 抄紙 系内での填料等の堆積及び汚れが発生し、 そのため抄紙機の運転を 停止して抄紙機を洗浄する頻度が増加し、 生産効率を著しく低下さ せ、 更には、 填料等の堆積及び汚れに起因するかすが紙に抄き込ま れ、 紙の品質低下等の問題点も生じている。 そこで、 二酸化チタン の紙への含有歩留ま りを向上させる 目的で、 ポリ アク リルアミ ド、 ポリ アミ ドポリ アミ ンェピク ロ ロ ヒ ドリ ン、 ポリ エチレンイ ミ ン等 の歩留向上剤が使用されている。 更に近年、 水溶性歩留向上剤を単独で使用するときよ りもさ らに 高い歩留まり向上効果を得る方法と して、 両性ポリ アク リルアミ ド 系共重合体と、 カチオン性基を有するポリ アク リ ルァミ ド系ポリ マConventionally, calcium carbonate, titanium dioxide, hydrated carboxylic acid (white carbon), talc, clay, kaolin, and urea have been used to improve the optical properties such as whiteness and opacity of paper, or the printability of paper. Fillers for papermaking, such as fine particles of mono- marine polymer, are used. Among these fillers, titanium dioxide has a high light scattering ability, and is therefore widely used for imparting high opacity to paper. However, titanium dioxide has a large problem in that the yield when making paper with a paper machine is extremely low because of its small particle size even when compared with other papermaking fillers. If the yield of the filler is low, the accumulation of the filler and the like in the papermaking system and dirt occur, so that the frequency of stopping the operation of the papermaking machine and washing the papermaking machine increases, thereby significantly reducing the production efficiency. In the case of paper, debris resulting from the accumulation of fillers and dirt is incorporated into the paper, which causes problems such as deterioration of paper quality. Therefore, in order to improve the yield of titanium dioxide contained in paper, retention aids such as polyacrylamide, polyamide polyamine chlorohydrin, and polyethyleneimine are used. . Furthermore, in recent years, as a method of obtaining a higher yield improving effect than when a water-soluble retention aid is used alone, an amphoteric polyacrylamide copolymer and a polyacrylate having a cationic group are used. Release polymer
—とを用いる方法 （特開平 5— 7 8 9 9 7 ) , 両性水溶性重合体と ァニオン性コロイダルシリカおよび /あるいはベントナイ ト とを用 いる方法 （特開平 9— 1 9 5 1 9 7 ) など、 多様な提案がなされて いる。 (JP-A-5-78997), a method using an amphoteric water-soluble polymer and anionic colloidal silica and / or bentonite (JP-A-9-195197) Various proposals have been made.
しかし、 上記従来の歩留向上剤は、 填料の歩留ま り向上効果にお いても満足のできる状態にないだけでなく、 その添加率が一定水準 を超える と効果が平衡に達し、 抄紙系を汚すという欠点を有し、 又 、 薬品が高価であるという問題点も有している。 近年、 資源問題や 物流問題等に対応するため、 紙の軽量化が求められているため、 不 透明度対策として填料の歩留まりの向上が強く求められており、 更 に抄紙機の高速化、 白水のクローズド化なども強く求められている ため、 填料の歩留ま りの更なる向上に対する要求は年々高まってき ている。 発明の開示  However, the above-mentioned conventional retention aids are not only in a satisfactory state in terms of filler retention improvement effect, but when the addition ratio exceeds a certain level, the effect reaches equilibrium and papermaking It has the drawback of soiling and has the problem of expensive chemicals. In recent years, in order to respond to resource issues and logistics issues, the weight of paper has been required to be reduced.Therefore, it has been strongly required to improve the yield of filler as a measure against opacity. Since there is a strong demand for closed containers, the demand for further improvement in filler yield is increasing year by year. Disclosure of the invention
本発明の目的は、 セルロース繊維、 硫酸アルミニウム及び二酸化 チタンを含有する紙を製造するに際し、 紙に対する二酸化チタンの 含有歩留まりを向上させ、 光学特性及び強度特性などに優れた紙の 製造方法を提供することにある。  An object of the present invention is to provide a method for producing paper containing cellulose fibers, aluminum sulfate and titanium dioxide, which improves the yield of containing titanium dioxide with respect to the paper and has excellent optical properties and strength properties. It is in.
上記目的は本発明の方法によ り達成することができる。  The above objects can be achieved by the method of the present invention.
本発明の紙の製造方法は、 セルロース繊維、 硫酸アルミ ニウム及 び二酸化チタンを含む紙料を抄紙工程に供して抄紙するに際し、 前記紙料を、 前記セルロース繊維を含む水性ス ラ リーに、 カルボ キシメチル基による置換度が 0 . 3〜 0 . 6に調整されているカル ポキシメチルセルロースを添加混合し、 その後に、 硫酸アルミニゥ ム及び二酸化チタンをさ らに添加混合することによって調製するこ とを特徴とするものである。 In the method for producing paper of the present invention, when a paper stock containing cellulose fibers, aluminum sulfate and titanium dioxide is subjected to a papermaking process to make paper, the stock is converted into an aqueous slurry containing the cellulose fibers by carbohydrate. The degree of substitution with the xymethyl group is adjusted to 0.3 to 0.6. It is characterized by being prepared by adding and mixing oxymethylcellulose, and then further adding and mixing aluminum sulfate and titanium dioxide.
本発明の紙の製造方法において 前記紙料に含まれる前記力ルボ キシメチルセル口ースの添加量を、 前記セル口ース繊維の絶乾質量 の 0 . 0 5〜 3 . 0質量0 /0にコ ン ト ロールすることが好ましい。 本発明の紙の製造方法において、 前記紙料に含まれる前記硫酸ァ ルミ二ゥムの添加量を、 前記セルロース繊維の絶乾質量の 0 . 1〜The amount of said force Rubo Kishimechiruseru port over scan contained in the paper stock in the papermaking process of the present invention, 0 the absolute dry weight of the cell opening over cellulose fiber. 0. 5 to 3.0 mass 0/0 It is preferable to control. In the paper production method of the present invention, the amount of the aluminum sulfate contained in the stock is 0.1 to 100% of the absolute dry mass of the cellulose fibers.
3 . 0質量％にコ ン ト ロールすることが好ましい。 It is preferable to control the amount to 3.0% by mass.
本発明の紙の製造方法において、 前記紙料に含まれる前記二酸化 チタンの添加量を、 前記セルロース繊維の絶乾重量の 1〜 2 5質量 In the method for producing paper of the present invention, the amount of the titanium dioxide contained in the stock is 1 to 25 mass of the absolute dry weight of the cellulose fiber.
%にコントロールすることが好ましい。 発明を実施するための最良の形態 % Is preferably controlled. BEST MODE FOR CARRYING OUT THE INVENTION
本発明の発明者らは、 抄紙の際の二酸化チタンの含有歩留ま りを 、 安価に、 簡便に、 著しく 向上させることができ、 得られる紙の品 質 （光学的特性機械的強度特性など） を改善し得る方法について鋭 意研究を重ねてきた。 二酸化チタンの微粒子は、 一般にマイナスの 電荷を有し、 このため、 セルロース繊維シート （紙） に、 カチオン 性薬剤を介して、 静電気作用によ り吸着するものと考えられる。 本 発明者らは、 抄紙に際し、 セルロース繊維含有水性スラ リ ー中に、 予じめ、 カルボキシメチル基による置換度が 0 . 3〜 0 . 6に調製 されているカルボキシメチルセルロースを添加混合しておき、 その 後に硫酸アルミニウム及び二酸化チタンをさらに添加混合すること によって、 抄紙用紙料を調製すると、 従来技術の上記問題点を解消 し得ることを見出し、 この発見に基いて本発明を完成させた。 これ は、 上記特定の置換度を有するカルボキシメチルセルロースを予じ めセル口ース繊維含有水性スラリ一に添加混合して、 セルロース繊 維にカルボキシメチルセルロースをなじませておき、 その後に硫酸 アルミニウムと ともに二酸化チタンを添加するこ とによって、 二酸 化チタン微粒子のセルロース繊維表面への付着が、 前記特定置換度 のカルボキシメチルセル口ースの静電気的作用によ り増幅されて、 二酸化チタン粒子の紙への含有歩留ま りが向上し、 それによつて所 望の光学的、 機械的強度特性を有する良質な紙が得られるためであ る。 The inventors of the present invention can remarkably improve the yield of titanium dioxide content at the time of papermaking inexpensively, easily, and significantly improve the quality of the obtained paper (such as optical properties and mechanical strength properties). We have been conducting intensive research on ways to improve). The fine particles of titanium dioxide generally have a negative charge, and therefore are considered to be adsorbed on the cellulose fiber sheet (paper) by a static action via a cationic agent. The present inventors have preliminarily added and mixed carboxymethylcellulose whose degree of substitution with carboxymethyl groups has been adjusted to 0.3 to 0.6 in a cellulose fiber-containing aqueous slurry before papermaking. Then, it was found that if the papermaking stock was prepared by further adding and mixing aluminum sulfate and titanium dioxide, the above problems of the prior art could be solved, and the present invention was completed based on this finding. This is because carboxymethylcellulose having the above specific degree of substitution is predicted. Carboxymethylcellulose is blended into the cellulose slurry containing cellulosic fiber, and carboxymethylcellulose is blended into the cellulose fiber, and then titanium dioxide is added together with aluminum sulfate to obtain cellulose fine particles of titanium dioxide. Adhesion to the fiber surface is amplified by the electrostatic action of the carboxymethyl cellulose having the specific degree of substitution, thereby improving the yield of titanium dioxide particles contained in the paper. This is because good quality paper having the above optical and mechanical strength characteristics can be obtained.
本発明方法に用いられる原料セルロース繊維は、 特に限定はなく 、 通常用いられている公知の製紙用パルプを用いることができ、 例 えばサルフアイ トパルプ、 クラフ トパルプ、 ソーダパルプ等のケミ カルパルプ、 セミケミカルパルプ、 メ力二カルパルプ等木材パルプ 、 或いは、 こ うぞ、 みつまた、 麻などの非木材パルプ、 古紙を処理 して製造される脱墨パルプなどを包含し、 かつ、 これらの未晒パル プ及び晒パルプを包含する。 但し、 製品と しての紙に良好な地合い が求められる場合は、 繊維長の短い広葉樹材を多量に配合すること が好ましい。  The raw material cellulose fiber used in the method of the present invention is not particularly limited, and generally used known papermaking pulp can be used. For example, chemical pulp such as sulfite pulp, craft pulp, and soda pulp, and semi-chemical pulp Pulp, wood pulp such as pulp, pulp, non-wood pulp such as kozo, honey, hemp, etc .; deinked pulp manufactured by processing waste paper; and unbleached pulp and bleached pulp. Pulp. However, when a good texture is required for the paper as a product, it is preferable to mix a large amount of hardwood having a short fiber length.
本発明方法に用いられる二酸化チタンは、 平均一次粒子径が 0 . ；!〜 0 . 4 μ πιの範囲内にあり、 結晶型はルチル型及びアナターゼ 型から選択され、 これらは単独に用いられてもよく或いは混合して 使用されてもよい。  The titanium dioxide used in the method of the present invention has an average primary particle diameter in the range of 0.1;! To 0.4 μπι, and the crystal form is selected from rutile type and anatase type, and these are used alone. Or may be used in combination.
二酸化チタンは、 予め水に分散した後紙料調製に供されるが、 前 記分散に際し、 粒子の再凝集を防止するために分散剤を添加しても よい。 分散剤と しては、 へキサメタ リ ン酸ソーダ、 ピロ リ ン酸ソ一 ダ、 ボリ アタ リル酸ソーダ等の 1種以上を用いることができる。 本発明方法において、 紙料に対する二酸化チタンの添加量は、 目 的とする紙の品質、 用途等に応じて適宜に設定することができるが 、 一般に、 紙料中のセルロース繊維の絶乾質量に対して、 1〜 2 5 質量％であることが好ましく、 3〜 2 0質量％であることが好まし い Titanium dioxide is preliminarily dispersed in water and then provided for preparation of a stock. In the above-mentioned dispersion, a dispersant may be added to prevent reaggregation of particles. As the dispersant, one or more of sodium hexamethacrylate, sodium pyrophosphate, sodium polyarylate and the like can be used. In the method of the present invention, the amount of titanium dioxide added to the paper stock can be appropriately set according to the quality of the target paper, the intended use, and the like. Generally, it is preferably from 1 to 25% by mass, more preferably from 3 to 20% by mass, based on the absolute dry mass of the cellulose fiber in the stock.
本発明方法に用いられるカルボキシメチルセルロース （以下 C M Cと記す) は、 木材パルプ、 又はリ ンターパルプ等を原料と し、 こ れにモノクロル酢酸等を反応させて合成されたセル口ース誘導体で あり、 工業的には水媒法、 溶媒法等の公知の製造方法で製造された ものをそのまま用いることができる。 CMCと類似のセルロース誘 導体であるカルボキシェチルセルロースを用いても、 本発明と同様 の効果は認められるけれども、 その効果は CMCと比較すると低く 、 又、 高価であるために、 本発明方法においては、 不可欠成分と し て用いる必要はない。  The carboxymethylcellulose (hereinafter referred to as CMC) used in the method of the present invention is a cellulose derivative derived from wood pulp or linter pulp as a raw material and reacted with monochloroacetic acid or the like. Industrially, those produced by a known production method such as an aqueous medium method and a solvent method can be used as they are. Although the same effects as those of the present invention can be obtained by using carboxyethylcellulose, which is a cellulose derivative similar to CMC, the effect is lower than that of CMC and the cost is high. Need not be used as an essential ingredient.
本発明方法に用いられる CMCの、 カルボキシメチル基置換度 （ エーテル化度） は、 0. 3〜 0. 6の範囲に調整される。 置換度が 0. 3未満のものは水に不溶であり、 セルロース繊維表面には吸着 されず、 単にセルロース繊維と混合されるだけであって、 二酸化チ タ ンの紙への歩留ま り を改善することができない。 また、 置換度が 0. 6を超えるものは、 分子内に存在するイオン性基 （一 CH2 C O O— 基） の数が過多になるため、 マイナス電荷を帯びているセル ロース繊維との静電的反発が強くなり 、 且つセルロース繊維との親 和性が乏しくなるため、 電解質が共存していて、 前記静電的反発が ある程度遮蔽されても、 セル口ース繊維表面への CM Cの吸着が不 十分となり、 このため、 二酸化チタンの紙への歩留ま り を改善する ことができない。 The degree of carboxymethyl group substitution (degree of etherification) of the CMC used in the method of the present invention is adjusted to the range of 0.3 to 0.6. Those having a degree of substitution of less than 0.3 are insoluble in water, are not adsorbed on the surface of cellulose fibers, are simply mixed with cellulose fibers, and have a high yield of titanium dioxide on paper. Can't improve. On the other hand, those with a degree of substitution exceeding 0.6 have an excessive number of ionic groups (one CH 2 COO— group) in the molecule, and therefore have a negative charge on the cellulose fiber with a negative charge. CCM adsorbs on the surface of the cell mouth fiber even if the electrolyte is co-existed and the electrostatic repulsion is shielded to some extent due to the strong repulsion and poor affinity with the cellulose fiber. And the yield of titanium dioxide on paper cannot be improved.
CMCのカルボキシメチル基置換度は後記の方法によ り測定する ことができる。  The degree of carboxymethyl group substitution of CMC can be measured by the method described below.
本発明方法に用いられる CMCは、 使用するセルロース繊維の性 状や前述のよ うに CMCの製造方法によ り様々な重合度のものが製 造可能であるが、 1 %水溶液の粘度が 5〜 1 6， 0 0 0 m P a - s ( 0. l N— N a C l溶媒、 2 5 °C、 B型粘度計） 、 平均重合度が 1 0 0〜 4 , 5 0 0、 平均分子量が 2万〜 1 0 0万の範囲のものを 用いることが好ましい。 本発明方法に用いられる CMCは、 一般に そのカルボン酸基が力ルポン酸ナト リ ゥム塩或いは力リ ゥム塩にさ れているものであり、 これを正確に記せばカルボキシメチルセル口 ースナ ト リ ゥム或レヽはカノレボキシメチノレセノレロース力 リ ゥムとすべ きものであるが、 慣用上、 ナト リ ウムやカ リ ウムの記載は省略し、 これを単にカルボキシメチルセルロース （CMC) と表示する。 本発明方法において用いられる、 CMCは、 そのナト リ ウム塩、 カリ ウム塩或いはアンモニゥム塩を包含するが、 価格が安く、 容易 に入手できること、 及び得られる効果が高いことなどによ り、 CM Cのナト リ ウム塩を用いることが好ましい。 又、 CMCをパルブス ラリーへ添加する際には、 CMCの水溶液が用いられるが、 この水 溶液の CMC濃度が高すぎると、 CMC水溶液の粘性が高く、 セル ロース繊維スラリー中への拡散が不良になるため、 CMC濃度は 0 . 〇 1〜 5. 0質量％であることが好ましく、 より好ましくは 0. 1〜 3. 0質量0 /0の範囲内である。 The CMC used in the method of the present invention depends on the properties of the cellulose fibers used. As described above, various polymerization degrees can be produced by the CMC production method, but the viscosity of a 1% aqueous solution is 5 to 16,000 mPa-s (0.1 l). N-NaCl solvent, 25 ° C, B-type viscometer), average polymerization degree of 100 to 4,500, average molecular weight of 20,000 to 100,000 Is preferred. The CMC used in the method of the present invention generally has a carboxylic acid group formed into a sodium salt or a sodium salt of a carboxylic acid. The bean or ray should be a canoleboxymethinoresenorelose-powered bead, but for simplicity, the description of sodium or calcium is omitted, and this is simply referred to as carboxymethylcellulose (CMC). I do. The CMC used in the method of the present invention includes its sodium salt, potassium salt or ammonium salt, but it is inexpensive, easily available, and highly effective. It is preferable to use a sodium salt. Also, when adding CMC to the pulverized slurry, an aqueous solution of CMC is used.If the CMC concentration of this aqueous solution is too high, the viscosity of the CMC aqueous solution is high, and diffusion into the cellulose fiber slurry becomes poor. becomes therefore, it is preferable that CMC concentration is 0.0 1 to 5.0 wt%, more preferably in the range of 0.1 to 3.0 mass 0/0.
CMCを溶解するための溶媒は一般に水であり、 本発明方法にお いても、 通常 CMCの水溶液が使用されるが、 CMCが安定に溶解 する範囲内で、 必要に応じて水と相溶性のある溶媒、 例えばメタノ ール、 エタノール等を水に対して 1 0. 0 ~ 3 0. 0 %の割合で混 合してもよいし、 更に CMCが安定して溶解する範囲で、 必要に応 じて芒硝等の電解質等の添加物質を混合してもよい。  The solvent for dissolving CMC is generally water, and in the method of the present invention, an aqueous solution of CMC is usually used. However, as long as the CMC is stably dissolved, the solvent may be compatible with water if necessary. Certain solvents such as methanol and ethanol may be mixed with water at a ratio of 10.0 to 30.0%, and if necessary, as long as CMC is stably dissolved. First, an additive such as an electrolyte such as sodium sulfate may be mixed.
本発明方法における C M Cの添加量は CMCの置換度、 製造す る紙の種類及び用途、 要求される性能等に応じて適宜設定すること ができるが、 セルロース繊維の乾燥質量に対して 0. 0 5〜 3. 0 質量％が用いられることが好ましく、 よ り好ましくは 0. 1〜 1 . 0質量％である。 C M Cの使用量が多ければ多いほど効果は顕著に なるが、 0. 0 5〜 3. 0質量。 /0の添加量で、 十分な効果が得られ 、 それが 3. 0質量％を超えると得られる紙の地合が不良になった り、 濾水性が不十分になる場合があり、 さ らに、 CMCは高価であ るため、 紙の用途や経済的な理由によ りその使用量に限度がある。 また CMCの添加量が、 0. 0 5質量％未満であると、 二酸化チタ ン含有歩留ま りの向上効果が不十分になることがある。 The amount of CMC added in the method of the present invention should be appropriately set according to the degree of substitution of CMC, the type and use of the paper to be produced, the required performance, etc. However, it is preferably used in an amount of 0.05 to 3.0% by mass, more preferably 0.1 to 1.0% by mass, based on the dry mass of the cellulose fiber. The effect becomes more remarkable as the amount of CMC used increases, but it is 0.05 to 3.0 mass. A sufficient effect can be obtained with the addition amount of / 0 , and if it exceeds 3.0% by mass, the formation of the obtained paper may be poor or the drainage may be insufficient. In addition, the cost of CMC limits its use due to paper applications and economics. If the amount of CMC is less than 0.05% by mass, the effect of improving the yield containing titanium dioxide may be insufficient.
CMC水溶液をセル口ース繊維スラ リ一に添加する際の、 セル口 ース繊維スラ リ ーのセルロース繊維濃度は、 固形分で 1. 0〜 5. 0質量％であることが好ましく、 よ り好ましく は 2. 0〜 4. 0質 量％である。 この濃度が高すぎると撹拌が困難で、 混合が不十分と なることがあり、 逆に濃度が低すぎると、 セルロース繊維と C M C との相互作用が不足し、 CMCのセルロース繊維表面への吸着が不 均一になることがある。  When the CMC aqueous solution is added to the cell mouth fiber slurry, the cellulose fiber concentration of the cell mouth fiber slurry is preferably 1.0 to 5.0% by mass in terms of solid content. More preferably, it is 2.0 to 4.0 mass%. If the concentration is too high, stirring may be difficult and mixing may be insufficient.On the other hand, if the concentration is too low, the interaction between cellulose fibers and CMC will be insufficient, and the adsorption of CMC to the surface of cellulose fibers will be insufficient. May be uneven.
本発明方法において、 紙料の調製に際し、 先ず、 セルロース繊維 の水性スラリーに C M Cを添加し、 その後、 硫酸アルミニウム及び 二酸化チタンを添加する。 硫酸アルミニウムと二酸化チタンの添加 順序は、 抄紙の際の添加状況に応じて適宜に定めればよい。 CMC の添加が、 硫酸アルミ ニウム及び二酸化チタ ンの添加後では、 パル プ繊維表面のマイナス電荷量は増加せず、 二酸化チタンの歩留ま り の向上効果が得られない。  In the method of the present invention, in preparing the stock, first, CMC is added to an aqueous slurry of cellulose fibers, and then aluminum sulfate and titanium dioxide are added. The order of addition of aluminum sulfate and titanium dioxide may be appropriately determined according to the state of addition during papermaking. After the addition of aluminum sulfate and titanium dioxide, the amount of negative charge on the pulp fiber surface does not increase, and the effect of improving the yield of titanium dioxide cannot be obtained.
本発明方法において、 二酸化チタン及び各種製紙用薬品の定着剤 として用いられる硫酸アルミ ニウムの添加量は、 紙の種類、 用途、 要求される品質に応じて適宜に設定することができるが、 パルプ繊 維の乾燥質量に対して 0. 1〜 3. 0質量％であることが好ましく 、 よ り好ましく は 1 . 0〜2 . 0質量0 /0である。 それが 0 . 1質量 %未満では二酸化チタ ンの定着能が不十分になることがあり、 又、 それが 3 . 0質量％を超えると、 経済的にも不利であるだけでなくIn the method of the present invention, the amount of titanium dioxide and the amount of aluminum sulfate used as a fixing agent for various papermaking chemicals can be appropriately set according to the type, use, and required quality of the paper. 0.1 to 3.0% by mass based on the dry mass of the fiber , Yo Ri preferably 1.0 to 2.0 mass 0/0. If it is less than 0.1% by mass, the fixing ability of titanium dioxide may be insufficient, and if it exceeds 3.0% by mass, not only is it economically disadvantageous but also
、 紙の地合の不良化及び保存性の悪化等を引き起こすことがある。 本発明方法においては、 製紙用紙力増強剤や湿潤紙力増強剤、 サ ィズ剤、 填料、 歩留向上剤、 染料、 消泡剤、 防腐剤、 粘度低下剤等 の公知抄紙用薬剤を、 必要に応じて紙料に添加することができ、 こ れらの種類及び添加量は、 得られる紙に必要とされる品質を満足で きる限り、 特に限定はない。 上記製紙用薬剤のそれぞれの効果を発 揮するには、 C M Cの添加後に添加されることが好ましい。 In some cases, the formation of the paper may be poor and the storage stability may be deteriorated. In the method of the present invention, known papermaking agents such as a papermaking paper strength enhancer and a wet paper strength enhancer, a sizing agent, a filler, a retention aid, a dye, an antifoaming agent, a preservative, and a viscosity reducing agent are used. They can be added to the stock as needed, and their type and amount are not particularly limited as long as the quality required for the obtained paper can be satisfied. In order to exert the respective effects of the above papermaking chemicals, it is preferable to add them after the addition of CMC.
本発明方法による紙の抄造は、 公知の湿式抄紙機、 例えば長網式 抄紙機、 ギャップフォーマ型抄紙機、 円網式抄紙機、 短網式抄紙機 等の商業規模の抄紙機を目的に応じて適宜選択し、 これに前記紙料 を供して実施される。  Papermaking by the method of the present invention can be carried out by using a known wet paper machine, for example, a commercial-scale paper machine such as a fourdrinier-type paper machine, a gap former-type paper machine, a circular net-type paper machine, or a short-mesh type paper machine. And the above-mentioned stock is supplied to this.
従来方法において得られる紙における二酸化チタンの歩留ま りに 対し、 本発明方法により、 それを約 1 0ポイ ント程度向上させるこ とができる。  The yield of titanium dioxide on paper obtained by the conventional method can be improved by about 10 points by the method of the present invention.
こ う して得られた原紙に、 各種サイズプレス装置、 ロールコータ 一等で澱粉、 P V A、 P A M等を用いてサイズ処理することは勿論 可能であるが、 製造速度の高速化を考慮した場合には、 フィルムメ タリ ングタイプのサイズプレス装置を用いて糊の固形濃度を高く し てサイズプレス処理を行う方法が好適に用いられる。 又、 ロールコ 一ター、 プレー ドコーター等の予備塗工を行う ことは勿論可能であ る。 又、 表面処理剤である澱粉、 Ρ λ^ Α、 P A M等に導電剤と して 種々の電解質を添加することも可能である。 電解質と しては、 芒硝 , 塩化ナ ト リ ウム等が挙げられる。  The base paper obtained in this way can be sized using starch, PVA, PAM, etc. with various size presses, roll coaters, etc., of course. For the method, a method of performing a size press treatment by increasing the solid concentration of the paste by using a film-metering type size press device is preferably used. In addition, it is of course possible to perform preliminary coating of a roll coater, a plate coater, and the like. It is also possible to add various electrolytes as a conductive agent to the surface treatment agent starch, {λ ^}, PAM, and the like. Examples of the electrolyte include sodium sulfate, sodium chloride, and the like.
本発明方法によ り製造された紙は、 そのまま製品と して使用する こともでき、 又、 印刷用紙、 情報記録用紙等のように、 塗被組成物 層を有する紙の基紙と しても使用することができる。 実施例 Paper produced by the method of the present invention is used as it is as a product It can also be used as a base paper for paper having a coating composition layer, such as printing paper and information recording paper. Example
下記に実施例を挙げて、 本発明をより具体的に説明するが、 勿論 、 本発明はこれらに限定されるものではない。 尚、 下記の実施例及 び比較例において、 「％」 とあるのは、 すべて 「質量％」 であり、 セルロース繊維スラ リ ーへの添加剤の添加量は、 絶乾紙料質量に対 する 「質量％」 である。  Hereinafter, the present invention will be described more specifically with reference to Examples, but of course, the present invention is not limited thereto. In the following Examples and Comparative Examples, “%” means “% by mass” in all cases, and the amount of the additive added to the cellulose fiber slurry is based on the mass of the absolutely dry paper stock. "% By mass".
各物性は、 下記の方法によ り測定した。  Each physical property was measured by the following method.
験法  Test method
( 1 ) 引張強度  (1) Tensile strength
J I S P 8 1 1 3に準拠して測定し、 裂断長 （ k m) で示し た。  The measurement was carried out in accordance with JIS SP 8113 and indicated by the breaking length (km).
( 2 ) 白色度  (2) Whiteness
J I S P 8 1 4 8 ( I S O 2 4 7 0 ) に準拠して測定した  Measured according to JISP 8 1 4 8 (I S O 2 4 7 0)
( 3 ) 不透明度 (3) Opacity
J I S P 8 1 3 8に準拠して測定した。  The measurement was performed in accordance with JIS P8138.
( 4 ) 歩留ま りの計算  (4) Yield calculation
TA P P I T 2 6 9 - c m 9 2に準拠して紙料濃度及び灰分量 を測定した。  The stock density and ash content were measured according to TAPPIT 26 9-cm 92.
へッ ドボックス中全紙料濃度を HT、 ト レイ中全紙料濃度を WT 、 へッ ドボックス中灰分の 1 0 0分率を F 1、 白水中灰分の百分率 を F 2 と し、 全紙料 （繊維、 微細繊維、 填料） ワ ンパスリテンシ ョ ン （O P R) 及び填料ワ ンパス リ テンシ ョ ン （O P R) を次式に従 い算出した。 全紙料 O P R (%) = { (H T - WT) /H T } x 1 0 0 The total stock density in the headbox is HT, the total stock density in the tray is WT, the 100% fraction of ash in the headbox is F1, and the percentage of ash in white water is F2. Fiber, fine fiber, filler) The damper retention (OPR) and the filler damper retention (OPR) were calculated according to the following equations. Total stock OPR (%) = {(HT-WT) / HT} x 1 0 0
填料 O P R (%) = { (HT X F 1 - WT X F 2 ) /H T X F 1 } X 1 0 0  Filler O P R (%) = {(HT X F 1-WT X F 2) / H T X F 1} X 1 0 0
( 5 ) 紙中灰分測定  (5) Ash content measurement in paper
J I S P 8 1 2 8 ( I S O 2 1 4 4 ) に準拠して測定した  Measured according to JISP 8 1 2 8 (I S O 2 1 4 4)
( 6 ) CMC溶液の粘度 (6) Viscosity of CMC solution
0. 1 N— N a C 1 を溶媒と して、 1 %溶液を調製し、 2 5 °Cに おいて B型粘度計で測定した。  A 1% solution was prepared using 0.1 N—NaCl as a solvent, and measured at 25 ° C with a B-type viscometer.
( 7 ) CMCのカルボキシメチル基による置換度の測定  (7) Measurement of degree of substitution of CMC by carboxymethyl group
絶乾した CMC約 0. 5 gを正確に秤量し、 これを磁製ルツボ中 で灰化した。 この灰を 5 0 0 m 1 ビーカーに移し、 これに水約 2 5 0 m l と、 1 / 1 0規定硫酸 3 5 m 1 とを加えて、 3 0分間煮沸し た。 煮沸液を冷却後、 フエノールフタ レイ ンを指示薬として加え、 さ らに過剰の 1 / 1 0規定硫酸を加えたのち、 1 Z 1 0規定水酸化 力 リ ウムで滴定を行った。  About 0.5 g of absolutely dried CMC was accurately weighed and incinerated in a porcelain crucible. The ash was transferred to a 500 ml beaker, and about 250 ml of water and 35 ml of 1/1 N sulfuric acid were added thereto, and the mixture was boiled for 30 minutes. After cooling the boiling liquid, phenolphthalein was added as an indicator, an excess of 1/10 N sulfuric acid was added, and then titration was performed with 1Z10N hydroxide.
供試カルボキシメチルセルロース （CMC) の置換度を次式に従 い算出した。  The degree of substitution of the test carboxymethylcellulose (CMC) was calculated according to the following equation.
A = ( a f 1 - b f 2 ) ZM—アルカ リ度  A = (a f 1-b f 2) ZM—degree of alkalinity
置換度 = 1 6 2 x A/ ( 1 0 0 0 0— 8 0 x A) .  Degree of substitution = 1 62 x A / (1 0 0 0 0-80 x A).
〔但し、 上記式中、 Aは試料 1 g中のアル力 リ に消費された 1 / 1 0規定の硫酸量 （m l ) を表し、 aは 1 / 1 0規定硫酸の添加量を 表し、 f 1 は 1 / 1 0規定硫酸のファクターを表し、 bは 1 Z 1 0 規定水酸化力リ ゥムの滴定量 (m l ) を表し、 f 2は 1 / 1 0規定 水酸化カリ ウムのファクターを表し、 Mは絶乾 CMCの質量 （ g ) を表す。 〕  [However, in the above equation, A represents the amount of 1/10 normal sulfuric acid (ml) consumed by the alcohol in 1 g of the sample, a represents the amount of 1/10 normal sulfuric acid added, and f 1 represents the factor of 1/10 normal sulfuric acid, b represents the titer (ml) of 1Z10 normal hydroxide power, and f2 represents the factor of 1/10 normal potassium hydroxide. And M represents the mass (g) of bone dry CMC. ]
実施例 1 実験用ナイアガラビータ一を用いて、 針葉樹晒クラフ トパルプと 広葉樹晒クラフ トパルプを 3対 7の比率で混合し、 カナダ標準フリ 一ネス （C S F) 4 0 0 m Lに叩解した。 このパルプ繊維の水性ス ラ リ ー （パルプ濃度 2. 0質量0 /0) に.， 置換度 0. 4 6の CMC ( 固形分濃度 1 . 0質董％の溶液粘度 2 0 m P a · s、 第一工業製薬 製試作品 4 5 O A) の 1. 0質量％濃度の水溶液を、 絶乾パルプ質 量に対し 0. 1 %の添加量で添加し、 十分に撹拌した。 更に、 撹拌 を続けたまま、 これにァニオン性ポリアク リルアミ ドを主成分とす る紙力増強剤 (商品名 ： ポリ アク ロ ン S T 1 3、 ミサヮセラミ ック 社製） 0. 5質量％、 製紙用強化ロジンサイズ剤 （商品名 ： S P E 、 荒川化学工業ネr'製） 0. 3質量％、 カチオン変性澱粉 （商品名 ： ケー ト 1 5、 ナショナルスターチ社製） 1 . 0質量％、 硫酸アルミ ニゥム 1. 5質量0 /0、 二酸化チタン （粒径 0. 2 / m、 アナターゼ 型、 商品名 ： B 1 0 1、 日本タルク社製） 1 7質量％を、 前記の順 で添加して紙料を調製した。 この紙料を用いて実験用角型シー トマ シンで坪量 9 0 g /m2 の紙を調製し、 室内にて送風乾燥した。 こ の手抄きシートを 2 3 °C、 5 0 % R Hの条件下 2 4時間調湿した後 、 品質評価試験に供した。 結果を表 1 に示す。 Example 1 Softwood bleached pulp and hardwood bleached pulp were mixed in a ratio of 3: 7 using an experimental Niagara Vita and beaten to 400 mL of Canadian Standard Freeness (CSF). Aqueous scan la rie of the pulp fibers (pulp concentration 2.0 mass 0/0)., Degree of substitution 0.4 6 CMC (solids concentration 1. Solution viscosity 2 0 0 TadashiTadashi% m P a · An aqueous solution having a concentration of 1.0% by mass of s and Daiichi Kogyo Seiyaku Co., Ltd., 45 OA) was added in an amount of 0.1% based on the absolute dry pulp mass, and thoroughly stirred. Further, with the stirring being continued, a paper strength agent containing anionic polyacrylamide as a main component (trade name: Polyaclon ST13, manufactured by Misa Ceramics) 0.5% by mass, papermaking Rosin sizing agent for use (trade name: SPE, Arakawa Chemical Industries, Ltd.) 0.3% by mass, cation-modified starch (trade name: Kate 15, National Starch Co., Ltd.) 1.0% by mass, aluminum sulfate Niumu 1.5 mass 0/0, titanium dioxide (particle diameter 0. 2 / m, anatase, trade name: B 1 0 1, Nippon talc Co., Ltd.) 1 7 wt%, was added in the order of the paper A preparation was prepared. Using this stock, paper having a basis weight of 90 g / m 2 was prepared using a square sheet machine for laboratory use, and air-dried indoors. The hand-made sheet was conditioned for 24 hours at 23 ° C. and 50% RH, and then subjected to a quality evaluation test. Table 1 shows the results.
実施例 2 Example 2
実施例 1 と同様にして手抄きシー トを作製し、 得られた紙を試験 して品質を評価した。 但し、 CMCと して、 置換度が 0. 6の CM C (固形分濃度 1 %の溶液粘度 5 0 0 m P a · s、 商品名セロゲン Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, as CMC, CMC with a degree of substitution of 0.6 (solution viscosity of 500% at a solid content of 1% 500 mPas, trade name cellogen)
HH、 第一工業製薬社製） を用いた。 試験結果を表 1 に示す。 HH, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Table 1 shows the test results.
実施例 3 Example 3
実施例 1 と同様にして手抄きシー トを作製し、 得られた紙を試験 して品質を評価した。 但し、 CMCの添加量をパルプ絶乾質量に対 して 1 . 5質量％と した。 試験結果を表 1 に示す。 実施例 4 Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, the amount of CMC added was 1.5% by mass with respect to the absolute pulp mass. Table 1 shows the test results. Example 4
実施例 1 と同様にして手抄きシー トを作製し、 得られた紙を試験 して品質を評価した。 但し、 CMCの添加量をパルプ絶乾質量に対 して 0. 0 5質量％と した。 試験結果を表 1 に示す。  Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, the amount of CMC added was set to 0.05% by mass based on the absolute pulp mass. Table 1 shows the test results.
実施例 5 Example 5
実施例 1 と同様にして手抄きシー トを作製し、 得られた紙を試験 して品質を評価した。 但し、 CMCと して、 固形分濃度 1 %の溶液 粘度が 9 0 0 m Pa * s、 置換度が 0. 4の CMC (商品名 ： セロ ゲン # 4 1 2 C、 第一工業製薬社製） を用いた。 試験結果を表 1 に 示す。  Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, the CMC is a CMC with a solution viscosity of 900 mPa * s at a solid concentration of 1% and a degree of substitution of 0.4 (trade name: Cellogen # 412C, manufactured by Daiichi Kogyo Seiyaku ) Was used. Table 1 shows the test results.
実施例 6 Example 6
実施例 1 と同様にして手抄きシートを作製し、 得られた紙を試験 して品質を評価した。 但し、 CMCと して、 固形分濃度 1 %の溶液 粘度 l O O m P a · s、 置換度が 0. 3 5の CMCを用い、 パルプ 繊維の絶乾質量に対する CM Cの添加量を 3. 0質量。/。、 硫酸アル ミニゥムの添加量を 1. 0質量％と した。 試験結果を表 1 に示す。 実施例 7  A handsheet was prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, as the CMC, a CMC with a solution viscosity of lOOmPas with a solid content of 1% and a substitution degree of 0.35 was used, and the amount of CMC added to the absolute dry mass of the pulp fiber was 3. 0 mass. /. The amount of aluminum sulfate added was 1.0% by mass. Table 1 shows the test results. Example 7
実施例 2 と同様にして手抄きシートを作製し、 得られた紙を試験 して品質を評価した。 但し、 パルプ繊維の絶乾質量に対する硫酸ァ ルミ二ゥムの添加率を 3. 0質量％と した。 試験結果を表 1に示す 実施例 8  Hand-made sheets were prepared in the same manner as in Example 2, and the obtained paper was tested to evaluate the quality. However, the addition ratio of aluminum sulfate to the absolutely dry mass of pulp fiber was 3.0 mass%. The test results are shown in Table 1.
実施例 1 と同様にして手抄きシー トを作製し、 得られた紙を試験 して品質を評価した。 但し、 パルプ繊維の絶乾質量に対する硫酸ァ ルミ二ゥムの添加量を 0. 1質量％と した。 試験結果を表 1に示す 比較例 1 実施例 1 と同様にして手抄きシー トを作製し、 得られた紙を試験 して品質を評価した。 但し、 紙料中に CMCを添加しなかった。 試 験結果を表 1 に示す。 Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, the amount of aluminum sulfate added to the absolutely dry mass of pulp fiber was 0.1% by mass. The test results are shown in Table 1 Comparative Example 1 Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, no CMC was added to the stock. Table 1 shows the test results.
比較例 2 Comparative Example 2
実施例 1 と同様にして手抄きシー トを作製し、 得られた紙を試験 して品質を評価した。 伹し、 紙料の調製において、 CMCの添加を 、 二酸化チタンの添加後と した。 試験結果を表 1 に示す。  Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. In addition, in the preparation of the stock, the addition of CMC was made after the addition of titanium dioxide. Table 1 shows the test results.
実施例 9 Example 9
実施例 1 と同様にして手抄きシー トを作製し、 得られた紙を試験 して品質を評価した。 但し、 CMCと して、 置換度が 0. 6の CM C (固形分濃度 1 %の溶液粘度 5 0 0 m P a · s、 商品名セロゲン HH、 第一工業製薬社製） を用い、 CMC添加率を 3. 3 %と した 。 試験結果を表 1 に示す。  Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, the CMC used was CMC with a degree of substitution of 0.6 (solution viscosity of 500 mPa · s with a solid concentration of 1%, trade name Serogen HH, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). The addition rate was 3.3%. Table 1 shows the test results.
比較例 3 Comparative Example 3
実施例 1 と同様にして手抄きシー トを作製し、 得られた紙を試験 して品質を評価した。 但し、 CMCと して置換度が 0. 7の CMC (固形分濃度 1 %の溶液粘度 7 5 0 m P a · s、 商品名セロゲン B S H 4、 第一工業製薬社製） を用いた。 試験結果を表 1 に示す。 実施例 1 0  Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, as the CMC, a CMC having a substitution degree of 0.7 (solution viscosity at a solid content of 1%: 750 mPa · s, trade name: Serogen BSH4, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used. Table 1 shows the test results. Example 10
実施例 9 と同様にして手抄きシー トを作製し、 得られた紙を試験 して品質を評価した。 但し、 CMC添加量を 0. 0 2 %と した。 試 験結果を表 1 に示す。  Hand-made sheets were prepared in the same manner as in Example 9, and the obtained paper was tested to evaluate the quality. However, the amount of CMC added was 0.02%. Table 1 shows the test results.
比較例 4 Comparative Example 4
比較例 1 と同様にして手抄きシー トを作製し、 得られた紙を試験 して品質を評価した。 但し、 紙料の調製に際し、 パルプ繊維絶乾質 量に対し、 カチオン性ポリ アク リルアミ ドを成分とする歩留向上剤 (商品名 ： ハイモロ ック D R 1 2 0 0 H、 ハイモ社製） 0. 0 4質 量％を、 二酸化チタ ンの添加後に添加した。 試験結果を表 1 に示す 比較例 5 A handsheet was prepared in the same manner as in Comparative Example 1, and the obtained paper was tested to evaluate the quality. However, in preparing the paper stock, a retention improver containing a cationic polyacrylamide as a component (trade name: Himolock DR1200H, manufactured by Himo) is based on the absolutely dry pulp fiber content. . 0 4 quality % Was added after the addition of titanium dioxide. The test results are shown in Table 1 Comparative Example 5
比較例 1 と同様にして手抄きシー トを作製し 得られた紙を試験 して品質を評価した。 但し、 紙料の調製に際し、 パルプ繊維の絶乾 質量に対し、 カチオン性ポリ アク リルアミ ドを成分とする歩留向上 剤 （商品名 ： パーコール 5 7、 協和産業社製） 0 . 0 4質量％と、 変性ベントナイ ト (商品名 ： ハイ ドロコール 0、 協和産業社製) 0 . 1質量％とを、 二酸化チタ ンの添加後に添加した。 試験結果を表 1 に示す。  Hand-made sheets were prepared in the same manner as in Comparative Example 1, and the obtained paper was tested to evaluate the quality. However, when preparing the stock, the yield improver containing a cationic polyacrylamide as a component (trade name: Percoll 57, manufactured by Kyowa Sangyo Co., Ltd.) is 0.04% by mass based on the absolute dry mass of the pulp fiber. And 0.1% by mass of modified bentonite (trade name: Hydrocol 0, manufactured by Kyowa Sangyo Co., Ltd.) were added after addition of titanium dioxide. Table 1 shows the test results.
比較例 6 Comparative Example 6
実施例 1 と同様にして手抄きシー トを作製し、 得られた紙を試験 して品質を評価した。 但し、 硫酸アルミニウム添加量を、 パルプ繊 維絶乾質量に対して 0 . 0 5質量％と した。 試験結果を表 1 に示す 比較例 7  Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, the addition amount of aluminum sulfate was 0.05 mass% with respect to the dry weight of pulp fibers. The test results are shown in Table 1.Comparative Example 7
実施例 1 と同様にして手抄きシー トを作製し、 得られた紙を試験 して品質を評価した。 但し、 硫酸アルミニウム添加量を、 パルプ繊 維絶乾質量に対して 3 . 5質量％と した。 試験結果を表 1に示す。 Hand-made sheets were prepared in the same manner as in Example 1, and the obtained paper was tested to evaluate the quality. However, the amount of aluminum sulfate added was 3.5% by mass with respect to the dry mass of the pulp fibers. Table 1 shows the test results.
表 1 table 1
Figure imgf000016_0001
Figure imgf000016_0001
〔註〕 CMC添加順変更  [Note] CMC addition order changed
全紙料〇 PR 繊維、 微細繊維、 填料のワンパスリテンション (歩留まり） 填料〇PR 填料のワンパスリテンション （歩留まり）  One-pass retention of PR stock, PR fiber, fine fiber, filler (Yield) One-pass retention of PR filler (PR) (Yield)
4 カチオン性アクリルアミ ド歩留向上剤 （比較例 4)  4 Cationic acrylic amide retention improver (Comparative Example 4)
カチオン性アクリルアミ ド歩留向上剤 +ベントナイト （比較例 5) Cationic acrylic amide retention improver + bentonite (Comparative Example 5)
表 1から明らかな如く、 本発明の方法を用いれば、 二酸化チタン の歩留ま りが高く、 又、 紙質の優れた紙を、 容易に製造することが できる。 本発明方法では本発明方法用特定 C M Cを添加しない場合 と比較して、 二酸化チタンの歩留ま りの向上が見られ （実施例 1 比較例 1 ) 、 また、 他の歩留向上剤、 歩留向上システムを用いた場 合と比較しても、 その効果は高い （実施例 1、 比較例 4、 5 ) 。 C M Cの置換度は、 低い方が効果が高く、 置換度が 0 . 6を超える C M Cを用いた場合には、 効果が著しく低下する (実施例 1 、 5、 比 較例 3 ) 。 C M Cの添加順を最初にすることによ り、 その効果が発 現するが、 他の添加順では、 その効果が発現しない （実施例 1、 比 較例 2 ) 。 C M Cの添加量は高い方が、 効果は大きいが、 添加率を 3 . 0 %を越えて用いた場合には、 地合の悪化から紙力が比較的低 くなることがある （例えば実施例 1 、 3、 4、 6、 9、 1 0の対比 ) 。 硫酸アルミニウムの添加量は高いほど、 効果は高いが、 高すぎ ると却って紙の地合が低下して強度が低下することがある （例えば 実施例 1 、 7、 8、 比較例 6·、 7の対比） 。 産業上の利用可能性 As is clear from Table 1, the use of the method of the present invention makes it possible to easily produce titanium dioxide with high yield and excellent paper quality. In the method of the present invention, compared with the case where the specific CMC for the method of the present invention was not added, the yield of titanium dioxide was improved (Example 1 Comparative Example 1). The effect is high compared to the case where the retention improvement system is used (Example 1, Comparative Examples 4 and 5). The lower the degree of substitution of CMC, the higher the effect, and when CMC with a degree of substitution of more than 0.6 is used, the effect is remarkably reduced (Examples 1, 5 and Comparative Example 3). The effect appears when the order of addition of CMC is first, but does not appear when the order of addition of CMC is other (Example 1, Comparative Example 2). The higher the amount of CMC added, the greater the effect. However, if the addition ratio exceeds 3.0%, the paper strength may be relatively low due to deterioration of formation (for example, 1, 3, 4, 6, 9, 10). The higher the amount of aluminum sulfate added, the higher the effect. However, if it is too high, the paper formation may be reduced and the strength may be reduced (for example, Examples 1, 7, 8, Comparative Examples 6 and 7). Contrast). Industrial applicability
本発明方法は、 二酸化チタンの歩留ま り を向上させ、 優れた紙質 の紙を提供し、 且つ抄紙系内の清浄化をはかり操業性を向上させる 紙の製造方法であって、 高い有効性を有するものである。  The method of the present invention is a method for producing paper that improves the yield of titanium dioxide, provides paper of excellent paper quality, and cleans the papermaking system to improve operability. It has.

Claims

請 求 の 範 囲 The scope of the claims
1 . セルロース繊維、 硫酸アルミニウム及び二酸化チタンを含む 紙料を抄紙工程に供して抄紙するに際し、 1. When the paper stock containing cellulose fiber, aluminum sulfate and titanium dioxide is subjected to the papermaking process to make paper,
前記紙料を、 前記セル口ース繊維を含む水性スラ リーに、 カルボ キシメチル基による置換度が 0 . 3 〜 0 . 6に調整されているカル ボキシメチルセルロースを添加混合し、 その後に、 硫酸アルミ -ゥ ム及び二酸化チタンをさ らに添加混合することによって調製するこ とを特徴とする紙の製造方法。  The paper stock is mixed with an aqueous slurry containing cellulosic fibers, and carboxymethylcellulose whose degree of substitution with carboxymethyl groups is adjusted to 0.3 to 0.6, and then mixed with sulfuric acid. A paper production method characterized by being prepared by further adding and mixing aluminum-titanium and titanium dioxide.
2 . 前記紙料に含まれる前記カルボキシメチルセル口ースの添加 量を、 前記セルロース繊維の絶乾質量の 0 . 0 5 〜 3 . 0質量0 /0に コント口ールする、 請求の範囲第 1項に記載の紙の製造方法。 2. The amount of the carboxymethylcellulose port over scan contained in the stock, to 0. 0 5 1-3. Control port Lumpur 0 mass 0/0 of bone dry weight of the cellulose fibers, the claims 2. The method for producing paper according to item 1.
3 . 前記紙料に含まれる前記硫酸アルミニウムの添加量を、 前記 セルロース繊維の絶乾質量の 0 . 1 〜 3 . 0質量。/。にコン ト ロール する、 請求の範囲第 1項に記載の製造方法。  3. The addition amount of the aluminum sulfate contained in the stock is 0.1 to 3.0 mass of the absolute dry mass of the cellulose fiber. /. The production method according to claim 1, wherein the production method is controlled.
4 . 前記紙料に含まれる前記二酸化チタンの添加量を、 前記セル 口ース繊維の絶乾重量の 1 〜 2 5質量％にコン ト口ールする、 請求 の範囲第 1項に記載の紙の製造方法。  4. The control method according to claim 1, wherein the amount of the titanium dioxide contained in the stock is controlled to be 1 to 25% by mass of the absolute dry weight of the cellulosic fiber. Paper manufacturing method.
PCT/JP2003/003014 2003-03-13 2003-03-13 Process for producing paper WO2004081284A1 (en)

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CN102373649B (en) * 2010-08-23 2016-11-16 昆山钞票纸业有限公司 Production technology of paper and products thereof
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SE538863C2 (en) * 2015-05-22 2017-01-10 Innventia Ab Process for the production of paper or paperboard, paper or paperboard product obtained and uses thereof
EP3315659A1 (en) * 2016-10-27 2018-05-02 Kelheim Fibres GmbH Man-made cellulosic fibre and nonwoven product or paper comprising the cellulosic fibre
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JPH073691A (en) * 1993-05-21 1995-01-06 Tokushu Paper Mfg Co Ltd Filled paper
JPH08246389A (en) * 1995-03-10 1996-09-24 Kohjin Co Ltd Production of titanium paper
JP2003089994A (en) * 2001-09-13 2003-03-28 Oji Paper Co Ltd Method for making paper

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JPS5860099A (en) * 1981-10-06 1983-04-09 株式会社　興人 Production of neutralized decorative paperboard with improved yield of titanium dioxide and pigment
JPH073691A (en) * 1993-05-21 1995-01-06 Tokushu Paper Mfg Co Ltd Filled paper
JPH08246389A (en) * 1995-03-10 1996-09-24 Kohjin Co Ltd Production of titanium paper
JP2003089994A (en) * 2001-09-13 2003-03-28 Oji Paper Co Ltd Method for making paper

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